Liquid silicone resins

ABSTRACT

A liquid silicone resin composition is provided. The liquid silicone resin composition comprises (A) a polysiloxane, (B) a polyether alcohol compound, and optionally (C) an aminosilicon compound. The polysiloxane (A) comprises an MQ resin, which is dispersed in and optionally functionalized with the polyether alcohol compound (B), and which may also optionally have amino functionality. The liquid silicone resin composition comprises a tunable viscosity, which may range at 25° C. from 100 to 800,000 cps. A method of preparing the liquid silicone resin is also provided. The method comprises combining together a solid silicone resin and the polyether alcohol compound (B) to give a mixture comprising the polysiloxane (A) and the polyether alcohol compound (B), and liquefying the mixture, thereby preparing the liquid silicone resin composition. The method may optionally include the aminosilicon compound (C).

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and all advantages of U.S.Provisional Patent Application No. 63/107,643 filed on 30 Oct. 2020, thecontent of which is incorporated herein by reference

FIELD OF THE INVENTION

The present disclosure relates generally to silicone compositions and,more specifically, to a liquid silicone resin composition and methods ofpreparing the same.

DESCRIPTION OF THE RELATED ART

Silicones are polymeric materials used in numerous commercialapplications, primarily due to significant advantages they possess overtheir carbon-based analogues. More particularly referred to aspolymerized siloxanes or polysiloxanes, silicones include an inorganicsilicon-oxygen backbone chain (---—Si—O—Si—O—Si—O—---) having organicside groups attached to the silicon atoms. Organic side groups may beused to link two or more of these backbones together. By varying the—Si—O— chain lengths, side groups, and cross-linking, silicones can besynthesized with a wide variety of properties and compositions, withsilicone networks varying in consistency from liquid to gel to rubber tohard plastic. Silicone and siloxane-based materials are utilized inmyriad end use applications and environments, including as components ina wide variety of industrial, home care, and personal care formulations.

Silicone and siloxane-based materials are known in the art and areutilized in myriad end use applications and environments. The mostcommon silicone materials are based on the linear organopolysiloxanepolydimethylsiloxane (PDMS), a silicone oil. Such organopolysiloxanesare utilized in numerous industrial, home care, and personal careformulations. The second largest group of silicone materials is based onsilicone resins, which are formed with branched and cage-likeoligosiloxanes. Unfortunately, the use of siloxane-based materials incertain applications that may benefit from particular inherentattributes of organopolysiloxanes (e.g. low-loss and stable opticaltransmission, thermal and oxidative stability, etc.) remains limited dueto the weak mechanical properties of conventional silicone networkssuitable for functionalization and/or further reaction, which maymanifest in materials with poor or unsuitable characteristics such aslow tensile strength, low tear strength, etc. Moreover, as conventionalsilicone networks and carbon-based polymers are often incompatibleand/or possess antagonistic properties with respect to one another,additional research is needed to identify useful ways for efficientlyand effectively functionalizing silicones, such as silicone resins.

For example, many conventional silicone materials (e.g. siloxanes,silicone resins) are hydrophobic, and are thus difficult to mix withpolar organic materials under a wide range of conditions. As such, thesesilicone materials are typically utilized in either solid forms or,where a solution/dispersion is necessary, with apolar organic (e.g.hydrocarbon) solvents such as benzene, toluene, ethylbenzene, andxylenes (i.e., BTEX solvents). Unfortunately, such conditions are alsooften incompatible with certain polar organic materials, as well as theprocess conditions necessary for their use. Moreover, the nature of BTEXsolvents, which present numerous environmental and health-relatedconcerns, necessitates further exploration for safe and effective use ofsilicone materials in nontraditional applications.

BRIEF SUMMARY OF THE INVENTION

A liquid silicone resin composition (the “composition”) is disclosed.The composition comprises (A) a polysiloxane having the followinggeneral formula:

(R¹ ₃SiO_(1/2))_(a)(R²₂SiO_(2/2))_(b)(R′R²SiO_(2/2))_(b′)(R²SiO_(3/2))_(c)(R′SiO_(3/2))_(c′)(SiO_(4/2))_(d),

wherein subscripts a, b, b′, c, c′ and d are each mole fractions suchthat a+b+b′+c+c′+d=1, with the provisos that 0<a<1, 0≤b<0.2, 0≤b′≤0.10<c<0.2, 0≤c′≤0.1, 0<d<1, 0≤b′+c′≤0.1, and the ratio of subscript a tosubscript d is from 0.5 to 1.5 (a:d); each R¹ is independently selectedfrom hydrocarbyl groups having from 1 to 30 carbon atoms, —OH, and H;each R² is independently selected from R¹ and —OX, where each X isindependently H, a hydrocarbyl group R having from 1 to 30 carbon atoms,or a polyether moiety having the general formula —Y—R³(—[Y]_(j)—Z)_(i),wherein R³ is a substituted or unsubstituted hydrocarbon segment, each Yis an independently selected oxyalkylene segment of general formula(C_(n)H_(2n)O)_(m), where subscript m is from 1 to 50 and subscript n isindependently selected from 2 to 4 in each moiety indicated by subscriptm, each Z is independently H or a resinous silicone moiety, subscript iis from 0 to 8, and subscript j is independently 0 or 1 in each moietyindicated by subscript i; and each R′ comprises an independentlyselected amino group. The composition also comprises (B) a polyetheralcohol compound having the general formula HO—Y—R³(—[Y]_(j)—Z)_(i),wherein each Y, R³, Z, subscript j, and subscript i are as definedabove.

A method of preparing the liquid silicone resin composition is alsodisclosed. The method comprises (I) combining together a solid siliconeresin and the polyether alcohol compound (B) to give a mixturecomprising the polysiloxane (A) and the polyether alcohol compound (B).The solid silicone resin has the following general formula:

(R¹ ₃SiO_(1/2))_(a)(R⁴ ₂SiO_(2/2))_(b)(R⁴SiO_(3/2))_(c)(SiO_(4/2))_(d),

where each R⁴ is independently selected from R¹ and —OR, with theproviso that R⁴ is selected from —OH and —OR in at least one T siloxyunit indicated by subscript c, and each R¹, R, and subscripts a, b, c,and d are as defined above. The method also comprises (II) liquefyingthe mixture comprising the polysiloxane (A) and the polyether alcoholcompound (B), thereby preparing the liquid silicone resin composition.The method may optionally utilize (C) an aminosilicon compound.

DETAILED DESCRIPTION OF THE INVENTION

A liquid silicone resin composition (the “composition”) is providedherein, along with a method of preparing the same. As will be understoodfrom the description herein, the composition provides a functional MQresin, optionally capped with one or more polyether-containing moieties,in a liquid form without need for solvents or other carrier vehicles. By“liquid”, it is meant that the composition is flowable and has aviscosity that can be measured at 25° C. The particular materials andconditions utilized provide the composition with a highly-tunable liquidviscosity, thereby providing the composition numerous uses in myriadcompositions and methods, including in preparing curable compositions(e.g. such as those based on one or more silicones) and variouscomponents thereof. Moreover, owing to the unique structural features,the liquid composition may be suitable for dispersion into water,polyols, or other polar liquid formulations (e.g. those containinganionic and/or non-ionic surfactants).

The composition generally includes (A) a polysiloxane, (B) a polyetheralcohol compound, and optionally (C) an aminosilicon compound, which aredescribed in turn below, along with additional compounds that may bepresent in the composition which may be collectively referred to hereinas the “components” of the composition (i.e., “component (A)”,“component (B)”, etc., respectively.) or, likewise, as “compound(s),”and/or “reagent(s)” (A) and/or (B), etc.

As understood by those of skill in the art, siloxanes may becharacterized in terms of [M], [D], [T], and/or [Q] units/siloxy groupstherein. More specifically, these [M], [D], [T], and [Q] siloxy groupseach represent structural units of individual functionality present inpolysiloxanes, such as organosiloxanes and organopolysiloxanes. Inparticular, [M] represents a monofunctional unit of general formulaR″₃SiO_(1/2); [D] represents a difunctional unit of general formulaR″₂SiO_(2/2); [T] represents a trifunctional unit of general formulaR″SiO_(3/2); and [Q] represents a tetrafunctional unit of generalformula SiO_(4/2), as shown by the general structural moieties below:

In these general structural moieties, each R″ is independently amonovalent or polyvalent substituent. As understood in the art, specificsubstituents suitable for each R″ are not particularly limited, and maybe monoatomic or polyatomic, organic or inorganic, linear or branched,substituted or unsubstituted, aromatic, aliphatic, saturated orunsaturated, and combinations thereof. Typically, each R″ isindependently selected from hydrocarbyl groups, alkoxy and/or aryloxygroups, and siloxy groups, such as those represented by any one, orcombination, of [M], [D], [T], and/or [Q] units described above.

As introduced above, the composition comprises the polysiloxane (A). Aswill be appreciated in view of the description herein, the polysiloxane(A) may be categorized or otherwise referred to as an MQ resin where, asintroduced above, M designates monofunctional siloxy units (i.e.,R″₃SiO_(1/2), with R″ representing a silicon-bonded substituent) and Qdesignates tetrafunctional siloxy units (i.e., SiO_(4/2)). Such MQresins are known in the art as macromolecular polymers composedprimarily of M and Q units and, optionally a limited number of D and/orT units (e.g. s 20 mole %, total), and typically present in/as a solid(e.g. powder or flake) form unless disposed in a solvent. These MQresins are often designated simply by the general formula [M]_(x)[Q]where subscript x refers to the molar ratio of M siloxy units to Qsiloxy units when the number of moles of Q siloxy units is normalizedto 1. In such instances, the greater the value of x, the lesser thecrosslink density of MQ resin. The inverse is also true as, when thevalue of x decreases, the number of M siloxy units decreases, and thusmore Q siloxy units are networked without termination via an M siloxyunit. It will be appreciated, however, that the normalized content of Qsiloxy units does not imply or limit MQ resins to only one Q unit.Rather, MQ resins typically includes a plurality of Q siloxy unitsclustered or bonded together, as will be appreciated from thedescription below.

Typically, the polysiloxane (A) has the following general formula:

(R¹ ₃SiO_(1/2))_(a)(R²₂SiO_(2/2))_(b)(R′R²SiO_(2/2))_(b′)(R²SiO_(3/2))_(c)(R′SiO_(3/2))_(c′)(SiO_(4/2))_(d),

wherein subscripts a, b, b′ c, c′, and d are each mole fractions suchthat a+b+b′+c+c′+d=1, with the provisos that 0<a<1, 0≤b<0.2, 0≤b′≤0.1,0<c<0.2, 0≤c′≤0.1; 0<d<1, 0≤b′+c′≤0.1, and the ratio of subscript a tosubscript d is from 0.5 to 1.5 (a:d); each R¹ is independently selectedfrom hydrocarbyl groups having from 1 to 30 carbon atoms, —OH, and H;each R² is independently selected from R¹ and —OX, where each X isindependently H, a hydrocarbyl group R having from 1 to 30 carbon atoms,or a polyether moiety as described below; and each R′ comprises anindependently selected amino group.

With reference to the general formula of the polysiloxane (A) above,hydrocarbyl groups suitable for R¹ include monovalent hydrocarbonmoieties, as well as derivatives and modifications thereof, which mayindependently be substituted or unsubstituted, linear, branched, cyclic,or combinations thereof, and saturated or unsaturated. With regard tosuch hydrocarbyl groups, the term “unsubstituted” describes hydrocarbonmoieties composed of carbon and hydrogen atoms, i.e., without heteroatomsubstituents. The term “substituted” describes hydrocarbon moietieswhere either at least one hydrogen atom is replaced with an atom orgroup other than hydrogen (e.g. a halogen atom, an alkoxy group, anamine group, etc.) (i.e., as a pendant or terminal substituent), acarbon atom within a chain/backbone of the hydrocarbon is replaced withan atom other than carbon (e.g. a heteroatom, such as oxygen, sulfur,nitrogen, etc.) (i.e., as a part of the chain/backbone), or both. Assuch, suitable hydrocarbyl groups may comprise, or be, a hydrocarbonmoiety having one or more substituents in and/or on (i.e., appended toand/or integral with) a carbon chain/backbone thereof, such that thehydrocarbon moiety may comprise, or be, an ether, an ester, etc. Linearand branched hydrocarbyl groups may independently be saturated orunsaturated and, when unsaturated, may be conjugated or nonconjugated.Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic,and encompass cycloalkyl groups, aryl groups, and heterocycles, whichmay be aromatic, saturated and nonaromatic and/or non-conjugated, etc.Examples of combinations of linear and cyclic hydrocarbyl groups includealkaryl groups, aralkyl groups, etc. General examples of hydrocarbonmoieties suitably for use in or as the hydrocarbyl group include alkylgroups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups,and the like, as well as derivatives, modifications, and combinationsthereof. Examples of alkyl groups include methyl, ethyl, propyl (e.g.iso-propyl and/or n-propyl), butyl (e.g. isobutyl, n-butyl, tert-butyl,and/or sec-butyl), pentyl (e.g. isopentyl, neopentyl, and/ortert-pentyl), hexyl, and the like (i.e., other linear or branchedsaturated hydrocarbon groups, e.g. having greater than 6 carbon atoms).Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl,dimethyl phenyl, and the like, as well as derivatives and modificationsthereof, which may overlap with alkaryl groups (e.g. benzyl) and aralkylgroups (e.g. tolyl, dimethyl phenyl, etc.). Examples of alkenyl groupsinclude vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl,pentenyl, heptenyl, hexenyl, cyclohexenyl groups, and the like, as wellas derivatives and modifications thereof. General examples of halocarbongroups include halogenated derivatives of the hydrocarbon moietiesabove, such as halogenated alkyl groups (e.g. any of the alkyl groupsdescribed above, where one or more hydrogen atoms is replaced with ahalogen atom such as F or Cl), aryl groups (e.g. any of the aryl groupsdescribed above, where one or more hydrogen atoms is replaced with ahalogen atom such as F or Cl), and combinations thereof. Examples ofhalogenated alkyl groups include fluoromethyl, 2-fluoropropyl,3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl,5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl,2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl,3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, and the like, as well asderivatives and modifications thereof. Examples of halogenated arylgroups include chlorobenzyl, pentafluorophenyl, fluorobenzyl groups, andthe like, as well as derivatives and modifications thereof.

In certain embodiments, at least one R¹ is a substituted orunsubstituted hydrocarbyl group having from 1 to 30 carbon atoms. Forexample, in some such embodiments, the at least one R¹ is anindependently selected substituted or unsubstituted alkyl group, such asan alkyl group having from 1 to 24, alternatively from 1 to 18,alternatively from 1 to 16, alternatively from 1 to 12, alternativelyfrom 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6,carbon atoms. Specific examples of alkyl groups include methyl groups,ethyl groups, propyl groups (e.g. n-propyl and iso-propyl groups), butylgroups (e.g. n-butyl, sec-butyl, isobutyl, and tert-butyl groups),pentyl groups, hexyl groups, heptyl groups, etc., and the like, as wellas derivatives and/or modifications thereof. Examples of derivativesand/or modifications of such alkyl groups include substituted versionsthereof. For example, R¹ may comprise, alternatively may be, a hydroxylethyl group, which will be understood to be a derivative and/or amodification of the ethyl groups described above. Likewise, R¹ maycomprise, alternatively may be, an independently selected substituted orunsubstituted alkenyl groups having from 2 to 6 carbon atoms, such asfrom 2 to 5, alternatively from 2 to 4, alternatively from 2 to 3 carbonatoms. In certain embodiments, the polysiloxane (A) comprises at leasttwo R¹ groups comprising alkenyl functionality (i.e., at least two R¹are selected from substituted or unsubstituted alkenyl groups). In theseor other embodiments, each R¹ is independently selected from H, —OH,C1-C6 alkyl groups, aryl groups, alkenyl groups, phenyl groups, vinylgroups, and combinations thereof. In certain embodiments, at least 50,alternatively at least 60, alternatively at least 70, alternatively atleast 80, alternatively at least 90, mol % of all R¹ groups arehydrocarbyl groups.

With continued reference to the general formula of the polysiloxane (A)above, each R² is independently selected from R¹ and —OX, where each Xis independently H (i.e., such that R² is a hydroxy group), thehydrocarbyl group R having from 1 to 30 carbon atoms (i.e., such that R²is a hydrocarbyloxy group of formula —OR), or a polyether moiety. WhereX is the hydrocarbyloxy group, the hydrocarbyl group R may be selectedfrom any of the hydrocarbyl groups having from 1 to 30 carbon atoms setforth above. As such, examples of hydrocarbyloxy groups suitable for Xinclude alkoxy and aryloxy groups. Examples of alkoxy groups includemethoxy, ethoxy, propoxy, butoxy, benzyloxy, and the like, as well asderivatives and modifications thereof. Examples of aryloxy groupsinclude phenoxy, tolyloxy, pentafluorophenoxy, and the like, as well asderivatives and modifications thereof. In some embodiments, each R² isindependently selected from R¹ and —OR, where each R¹ is independentlyselected from H, —OH, and alkyl and aryl groups containing 1 to 30carbon atoms, and each R is independently selected from alkyl and arylgroups containing 1 to 30 carbon atoms. In these or other embodiments,each R² is independently selected from —OH and —OR, where each R isindependently selected from alkyl and aryl groups containing 1 to 30carbon atoms.

As introduced above, in certain embodiments, at least one R² is offormula and —OX, where X is the polyether moiety. In these embodiments,the polyether moiety is not particularly limited, and generallycomprises an oxyalkylene segment of general formula (C_(n)H_(2n)O)_(m),where subscript m is from 1 to 50 and subscript n is independently 2, 3,or 4 in each moiety represented by subscript m. In certain embodiments,subscript m is from 1 to 45, such as from 1 to 40, alternatively from 1to 30, alternatively from 1 to 25, alternatively from 1 to 20,alternatively from 1 to 15. In specific embodiments, subscript m is atleast 2, such that the polyoxyalkylene moiety may comprise one or moreoxyalkylene units selected from oxyethylene units (e.g. —(C₂H₄O)—, i.e.,where subscript n is 2), oxypropylene units (e.g. —(C₃H₆O)—, i.e., wheresubscript n is 3), and oxybutylene units (e.g. —(C₄H₈O)—, i.e., wheresubscript n is 4). When the oxyalkylene segment comprises more than onetype of oxyalkylene unit (i.e., is a polyoxyalkylene), the oxyalkyleneunits may be arranged in any fashion, such as in block form (e.g.ordered blocks and/or random blocks), randomized form, or combinationsthereof. In specific embodiments, the oxyalkylene segment comprises bothoxyethylene and oxypropylene units. In some such embodiments, theoxyalkylene segment is an oxyethylene-oxypropylene block copolymer.

The polyether moiety may comprise more than one oxyalkylene segment. Forexample, in certain embodiments, X comprises a polyether moiety havingthe general formula —Y—R³(—[Y]_(j)—Z)_(i), wherein R³ is a substitutedor unsubstituted hydrocarbon segment, each Y is an independentlyselected oxyalkylene segment of general formula (C_(n)H_(2n)O)_(m) asdescribed above, Z is a terminal group, subscript i is from 0 to 8, andsubscript j is independently 0 or 1 in each moiety indicated bysubscript i. In these embodiments, R³ is an at least divalenthydrocarbon linking group. More specifically, as used herein in thiscontext, the valency of the hydrocarbon segment R³ refers to the numberof substituents of subformula (—[Y]_(j)—Z) bonded thereto in addition tothe oxyalkylene segment Y. As such, the valency of the hydrocarbonsegment R³ in this context may be described as subscript i+1.

Typically, each hydrocarbon segment R³ independently comprises one ormore substituted or unsubstituted hydrocarbon groups, i.e., ahydrocarbon group that is optionally modified or substituted, e.g. withpendant alkoxy, carbonyl, siloxy, silyl, amino, amido, acetoxy, oraminoxy groups and/or internal O, N, or S atoms (i.e., in the backbone).For example, in some embodiments, the polysiloxane (A) comprises atleast one X corresponding to the general polyether moiety formula above,where the hydrocarbon segment R³ comprises, alternatively is, a linearor branched hydrocarbon group having from 3 to 30 carbon atoms,optionally comprising one or more aromatic groups, ether groups, aminegroups, or a combination thereof. In some such embodiments, thehydrocarbon segment R³ is a C1-C20 hydrocarbon group. In these or otherembodiments, each hydrocarbon segment R³ independently comprises anaromatic group, an ether group, an amine group, or a combinationthereof. As will be appreciated from the description herein, the etherand amine groups of the hydrocarbon segment R³ set forth above may beinternal (e.g. comprising an 0 or N atom in the backbone of the linearor branched hydrocarbon group) or pendant (e.g. comprising an alkoxy oramine group bonded to the backbone of the linear or branched hydrocarbongroup).

Each hydrocarbon segment R³ may be independently linear or branched.More specifically, as will be appreciated from the description herein,R³ typically comprises up to i number of branches (i.e., from 0 to 8branches), where subscript j is 1 for each branch off from R³ to theterminal group Z. In certain embodiments, each hydrocarbon segment R³comprises a branched hydrocarbon group having from 3 to 16 carbon atoms.In some embodiments, each oxyalkylene segment Y independently has theformula (C₂H₄O)_(x)(C₃H₆O)_(y)(C₄H₈O)_(z), where subscript x is from 1to 50, subscript y is from 0 to 50, and subscript z is from 0 to 50, andwhere units indicated by subscripts x, y and z may be in randomized orblock form in the oxyalkylene segment.

In some embodiments, the polysiloxane (A) comprises at least one Xcorresponding to the general polyether moiety formula above, wheresubscript i is 0 and each hydrocarbon segment R³ independently comprisesa linear or branched hydrocarbon group having from 3 to 30 carbon atoms.In these or other embodiments, the polysiloxane (A) comprises at leastone X where subscript i is 1 and the hydrocarbon segment R³ comprises atleast one group selected from linear or branched hydrocarbon groupshaving from 3 to 30 carbon atoms, phenols, tetrahydrofurans, and alkylamines, each optionally substituted with one or more alkoxy groups. Inthese or other embodiments, the polysiloxane (A) comprises at least oneX where subscript i is at least 2, and the hydrocarbon segment R³comprises at least one group selected from linear or branchedhydrocarbon groups having from 3 to 30 carbon atoms, alkyl amines,polyamines, polyamides, polyaziridines, polyphenols, and polyesters.

Typically, each terminal group Z is independently selected from H (i.e.,such that the polyether moiety is terminally hydroxy-functional) or aresinous silicone moiety (i.e., from condensation of terminalhydroxy-functionality with a condensable silicon-bonded moiety of thepolysiloxane (A)). For example, where subscript i is at least 1, theterminal group Z may represent a cross-link to another silanol group ofthe polysiloxane (A). Similarly, when i>1, the polysiloxane (A) maycomprise more than one cross-link. One of skill in the art willappreciate that the presence of such cross-linking in, as well as thecross-linking density of, the polysiloxane (A) in the compositiondepends on many factors, such as the hydroxyl (e.g. silanol)functionality of the silicone resin selected, the functionality of thepolyether alcohol compound (B) selected, the ratio of silicone resin topolyether alcohol compound (B) utilized to prepare the composition, thedegree of conversion, etc., as described below with respect to themethod. Likewise, the presence of such cross-linking can be ascertainedby methods known in the art, such as via rheological measurements of gelpoints due to the increase of average molecular weights in response tocross-linking (i.e., where the gel point indicates the weight-averagemolecular weight diverging toward infinity). For example, a rheometer(e.g. a rheometrics mechanical spectrometer using parallel plategeometry) may be utilized to carry out a frequency sweep experiment todetermine dynamic storage modulus, equilibrium modulus, and changes inmoduli during preparation of the composition. The full scope of theterminal group Z, as well as the potential for cross-linking of thepolysiloxane (A), will be better appreciated in view of the methoddescribed herein.

Each R′ independently comprises an amino group. In certain embodiments,each R′ is an amino group. The amino group of R′ may be of formula—N(H)_(f)R_(2-f), where each R is independently selected and definedabove, i.e., each R is an independently selected hydrocarbyl group, andwhere subscript f is independently 0, 1, or 2. In other embodiments,each R′ independently comprises a hydrocarbon group substituted with anamino group.

Suitable hydrocarbon groups are described above. In specificembodiments, each R′ independently comprises an aliphatic hydrocarbongroup substituted with an amino group.

The aliphatic hydrocarbon group can be linear or cyclic, and istypically saturated. In specific embodiments, each R′ comprises analkylamino group. For example, each R′ can be of formula—(CH₂)_(g)N(H)_(f)R_(2-f), where each subscript g is independently from1 to 30, alternatively from 1 to 25, alternatively from 1 to 20,alternatively from 1 to 15, alternatively from 1 to 10, alternativelyfrom 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4,alternatively from 2 to 4, and R′ and subscript f are defined above. Inspecific embodiments, subscript g is 3 and subscript f is 2 such thateach R′ is of formula —(CH₂)₃N(H)₂.

With continued reference to the general formula of the polysiloxane (A)above, subscripts a, b, b′, c, c′, and d are each mole fractions suchthat a+b+b′+c+c′+d=1. As will be appreciated by those of skill in theart, subscripts a, b, c, d, and e correspond to M, D, T, and Q siloxyunits, respectively. Both of subscripts b and b′ in the general formulaabove indicate D siloxy units, and both of subscripts c and c′ in thegeneral formula above indicate T siloxy units, but with differentsilicon-bonded substituents (R² vs. R′), respectively. In general,fraction of each siloxy unit is selected such that 0<a<1, 0≤b<0.2,0≤b′≤0.1, 0<c<0.2, 0≤c′≤0.1, 0<d<1, and 0≤b′+c′≤0.1, i.e., where thepolysiloxane (A) is optionally free from D siloxy units (including thoserepresented by subscripts b and/or b′), optionally free from T siloxyunits indicated by subscript c′, but comprises at least one each of M,T, and Q siloxy units (as indicated by subscripts a, c, and d). It willbe appreciated, however, that in such embodiments, the polysiloxane (A)will generally be configured such that R² is —OX in at least one,alternatively the majority, alternatively substantially all of, the Tsiloxy units indicated by subscript c and present therein. Likewise,while optionally free from D siloxy units, the polysiloxane (A) maycomprise a limited proportion of D siloxy units. Typically, however,subscripts b and c are less than 0.2, collectively (i.e., b+c:0.2). Incertain embodiments, subscript a is selected to be from 0.3 to 0.6. Inthese or other embodiments, subscript d is selected to be from 0.4 to0.7. In specific embodiments, subscript c′ is 0. In other embodiments,subscript c′ is from greater than 0 to 0.1, alternatively from greaterthan 0 to 0.05, alternatively from greater than 0 to 0.04, alternativelyfrom 0.01 to 0.04. In other specific embodiments, subscript b′ is 0. Inyet other embodiments, subscript b′ is from greater than 0 to 0.1,alternatively from greater than 0 to 0.05, alternatively from greaterthan 0 to 0.04, alternatively from 0.01 to 0.04. In further embodiments,b′ and c′ are each 0. In other embodiments, (b′+c′) is from greater than0 to 0.1, alternatively from greater than 0 to 0.05, alternatively fromgreater than 0 to 0.04, alternatively from 0.01 to 0.04.

It will be appreciated that subscripts a and d generally refer to the MQresinous portion of the polysiloxane (A), such that the ratio ofsubscript a to subscript d may be used to characterize the polysiloxane(A). For example, in some embodiments, the ratio of M siloxy unitsindicated by subscript a to Q siloxy units indicated by subscript d isfrom 0.5 to 1.5 (a:d). In these or other embodiments, the ratio of Msiloxy units indicated by subscript a to Q siloxy units indicated bysubscript d is from 0.7 to 1.2 (a:d).

As will be appreciated in view of the method further below, the featuresand properties of the polysiloxane (A) will be selected and controlledby the particular components utilized in preparing the liquid siliconeresin composition as a whole.

As introduced above, the composition also comprises the polyetheralcohol compound (B). Typically, the polyether alcohol compound (B) hasthe general formula HO—Y—R³(—[Y]_(j)—H)_(i), where each Y, R³, subscripti, and subscript j are as defined above. More specifically, R³ is asubstituted or unsubstituted hydrocarbon segment, each Y is anindependently selected oxyalkylene segment, subscript i is from 0 to 8,and subscript j is independently 0 or 1 in each moiety indicated bysubscript i. Additional description and examples of the polyetheralcohol compound (B) are provided below. However, as will be appreciatedin further detail in view of the method described herein, the groupsindicated by Y and R³ in the general formula of the polyether alcoholcompound (B) are the same (i.e., in terms of scope) as those same groupsindicated above with respect to the polyether moiety of the polysiloxane(A). As such, the description of each Y and R³, as well as the moietiesindicated by subscripts j and i, applies equally to the conservedportions of the formulae of both the polyether moiety of thepolysiloxane (A) and the polyether alcohol compound (B).

In general, the polyether alcohol compound (B) comprises thealkoxylation reaction product of (b-1) a compound comprising at leastone alkoxylatable group (e.g. a functional group comprising a labilehydrogen atom bonded to a nucleophilic O, N, or S atom, such as an —OH,—NH, or SH group) (i.e., an alkoxylatable compound (b-1)), and (b-2) analkoxylation agent (e.g. an alkylene oxide, polyoxyalkylene compound,etc.) which are described in turn below. As will be understood by thoseof skill in the art, the alkoxylation reaction is not limited, and willbe selected in view of the particular alkoxylatable compound (b-1) andalkoxylation agent (b-2) utilized.

Typically, the alkoxylatable compound (b-1) is an organic alcohol, i.e.,an organic compound comprising a carbon backbone and at least onehydroxyl (i.e., —OH) group. In such embodiments, the alkoxylatablecompound (b-1) may be referred to more specifically as an alcoholcompound (b-1). As will be understood in view of the examples anddescription below, the alcohol compound (b-1) may be a mono-ol (i.e.,comprise but one hydroxyl functional group) or a polyol (i.e., compriseat least two hydroxyl groups), such as a diol, triol, etc. The carbonbackbone of the alcohol compound (b-1) may be substituted orunsubstituted, e.g. with any of the functional groups described herein.When substituted, the carbon backbone of the alcohol compound (b-1) maycomprise pendant substitutions (i.e., in place of hydrogen atomsattached to the carbon backbone) or substitutions of carbon atoms withinthe backbone itself (e.g. by other heteroatoms, such as O, S, N, etc.).As such, it is to be appreciated that, while characterized or otherwisereferred to as an organic alcohol, the alcohol compound (b-1) may bealternatively or further defined in view of additional functionalitywhen present (e.g. as an amino alcohol, etc.). Additionally, the carbonbackbone may be linear or branched, and may thus comprise linear,branched, and/or cyclic hydrocarbon segments.

As will be understood in view of the description herein, the alcoholcompound (b-1) typically corresponds to the general formulaHO—R³(—OH)_(i), where R³ and subscript i are as defined above. Morespecifically, R³ is a hydrocarbon segment and subscript i is from 0 to8. In such embodiments, it will be appreciated that the hydrocarbonsegment R³ represents the carbon backbone of the alcohol compound (b-1),which, as indicated by subscript i, may comprise may comprise from 0 to8 hydroxyl groups in addition to the required hydroxyl group.

In certain embodiments, subscript i is 0, such that the alcohol compound(b-1) is an alcohol of general formula HO—R³. In some such embodiments,R³ comprises, alternatively is, a linear or branched hydrocarbon grouphaving from 3 to 30 carbon atoms. For example, in some embodiments, R³is a branched hydrocarbon group having from 3 to 30 carbon atoms.

In some such embodiments, alcohol compound (b-1) has the formula:

where R⁵, R⁶, and R⁷ are independently selected from C1-C13 alkylgroups. For example, in some such embodiments, R⁵ and R⁶ are eachindependently selected from C1-4 alkyl groups, and R⁷ is H or a C1-C13alkyl group. In some of these embodiments, R³ comprises a total of from7 to 16 carbon atoms, such as from 9 to 12 carbon atoms. In someembodiments, R³ comprises a branching degree of at least 3. In thiscontext, the term “branching degree” as used herein means the totalnumber of methyl (—CH₃) groups minus 1. For instance, an R³ comprisingan alkyl group comprising four methyl group substituents comprises abranching degree of 3. In some embodiments, R⁵ is an alkyl groupcomprising from 3 to 12 carbon atoms, such a C3-C8 alkyl group, or,alternatively, a C4-C6 alkyl group. In such embodiments, R⁵ comprises atleast 2 methyl groups. In these or other embodiments, R⁶ is an alkylgroup comprising from 3 to 12 carbon atoms, such as a C4-C10 alkylgroup, alternatively a C6-C8 alkyl group. In some embodiments, R⁷comprises at least 2 methyl groups. For example, in certain embodiments,R⁷ is a C1-C3 alkyl group. In other embodiments, R⁷ is H. In someembodiments, R⁵ is CH₃(CH₂)₂CH(CH₃)(CH₂)₂CH(CH₃), and R⁶ is H, and R⁷ isCH₃. In specific embodiments, the alcohol compound (b-1) is(3-methyl-6-ethyl)-2-nonanol.

In certain embodiments, subscript i is 1, such that the alcohol compound(b-1) is a diol of general formula HO—R³—OH, where the hydrocarbonsegment is a divalent linking group. In certain embodiments, forexample, R³ comprises, alternatively is, an alkyl group (i.e., such thatthe alcohol compound (b-1) is a glycol) or substituted alkyl group (e.g.a diethylamino group, such that the alcohol compound (b-1) is adiethanolamine), an aryl group (e.g. a phenyl, benzyl, tolyl, etc.), atetrahydrofuran group, or other difunctional materials, such as thosederived from ring opening of epoxy adducts or alkoxy diols.

In particular embodiments, subscript i is 2, such that the alcoholcompound (b-1) may be further defined as a polyol, such as a triol,tetraol, etc. In such embodiments, the alcohol compound (b-1) isexemplified by glycerols, pentaerythritols, sugar alcohols (e.g.sorbitol, xylitol, mannitol, etc.), and the like. In some suchembodiments, R³ comprises, alternatively is selected from alkyl amines,polyamines, polyamides, polyaziridines, polyphenols, and polyesters. Insome embodiments, for example, R³ comprises, alternatively is, a phenolformaldehyde resin, an epoxy adduct of a glycidyl ether with a polyol,an epoxy adduct of a glycidyl ether with a diamine or polyamine (e.g.such as a secondary diamine). In any of such embodiments, subscript imay be from 2 to 8, such that alcohol compound (b-1) comprises from 2 to8 hydroxyl groups, such as from 3 to 8, alternatively 3 to 6,alternatively from 3 to 5, hydroxyl groups.

It is to be appreciated that the other polyols and alcohols may be usedas the alcohol compound (b-1) to prepare the polyether alcohol compound(B) as well. For example, in certain embodiments, the alcohol compound(b-1) is selected from polyether polyols, polyester polyols,polycarbonate polyols, acrylic polyols, polyols derived from isocyanatepre-polymers (e.g. those having a functionality from 2 to 8, etc.), andthe like.

The alkoxylation agent (b-2) is not limited, and may be or include anyalkoxylation compound suitable for substituting the alkoxylatablecompound (b-1) to give the polyether alcohol compound (B) as describedherein. Typically, the alkoxylation agent (b-2) is selected fromalkylene oxides, polyoxyalkylene compounds, and combinations thereof.For example, in certain embodiments, the alkoxylation agent (b-2) isselected from ethylene oxide, propylene oxide, butylene oxide, andcombinations thereof. In other embodiments, the alkoxylation agent (b-2)is selected from polyoxyethylenes, polyoxypropylenes, polyoxybutylenes,and combinations thereof (e.g. in the form of random or block polymers).

One of skill in the art will appreciate that the term “alkoxylation” asused herein, e.g. with regard to precursors (b-1) and (b-2) of thepolyether alcohol compound (B), may be considered functional and/ordescriptive, and includes ethers/etherification products as well.

It will be appreciated by those of skill in the art that the number ofhydroxyl groups present on the alkoxylatable compound (b-1) willinfluence the overall structure of the polyether alcohol compound (B)itself. In particular, the polyether alcohol compound (B) may compriseup to i=1 polyoxyalkylene groups, i.e., from alkoxylating thealkoxylatable group(s) of the alcohol compound (b-1) with thealkoxylation agent (b-2).

With regard to the polyether alcohol compound (B) itself, e.g.corresponding to the general formula HO—Y—R³(—[Y]_(j)—H)_(i), eachoxyalkylene segment Y may independently have the formula(C₂H₄O)_(x)(C₃H₆O)_(y)(C₄H₈O)_(z), where subscript x is from 1 to 50,subscript y is from 0 to 50, and subscript z is from 0 to 50, and whereunits indicated by subscripts x, y and z may independently be inrandomized or block form in each oxyalkylene segment. In certainembodiments, in each oxyalkylene segment Y, subscript x is from 1 to 20,subscript y is from 0 to 20, and subscript z is from 0 to 20. In somesuch embodiments, x+y+z=from 1 to 50, such as from 1 to 20,alternatively from 10 to 20. In specific embodiments, subscript x isfrom 2 to 20, and subscripts y and z are both 0, such that the polyetheralcohol compound (B) may be further defined as a polyoxyethylenealcohol.

In certain embodiments, the polyether alcohol compound (B) is a nonionicsurfactant.

For example, in some such embodiments, the polyether alcohol compound(B) may be selected from straight-chain linear ethoxylates, branchedethoxylates (e.g. polyethylene glycolp-(1,1,3,3-tetramethylbutyl)-phenyl ether), amine ethyoxylates (e.g.tertiary amine ethoxylates, fatty amine ethoxylates and/orpropoxylates), ethoxylyated, propoxylated, and/or butoxylated glycols,and the like.

It will be appreciated from the description above that, in someembodiments, the polyether alcohol compound (B) may have the generalformula HO—(C₂H₄O)_(x)(C₃H₆O)_(y)(C₄H₈O)_(z)—CR⁵R⁶R⁷, where R⁵, R⁶, R⁷,and subscripts x, y, and z are as defined above. In some suchembodiments, for example, subscript x is from 1 to 40, subscripts y andz are selected such that y+z=1-6, R⁵ and R⁶ are independently selectedC1-C4 alkyl groups, and R⁷ is H or C1-C13 alkyl. In some suchembodiments, the moiety indicated by sub formula —CR⁵R⁶R⁷ comprises atotal of from 7 to 16 carbon atoms and a branching degree of at least 3.

In some embodiments, the polyether alcohol compound (B) has thefollowing formula:

where R⁸ is H or isopropyl; R⁹ is CH₃ or CH₂CH₃; subscript y′ is from 1to 5, such as from 1 to 4, alternatively from 2 to 4; and subscript x isfrom 2 to 30, such as from 2 to 20, alternatively from 2 to 10,alternatively from 2 to 9, alternatively from 5 to 9. In some of theseembodiments, R⁸ is H and R⁹ is CH₃, such that the polyether alcoholcompound (B) has the formula:

where subscripts y′ and x are as described above. In other embodiments,R⁸ is isopropyl, such that the polyether alcohol compound (B) has theformula:

where subscripts y′ and x are as described above.

In general, the polyether alcohol compound (B) may be prepared orotherwise obtained with a narrow molecular weight distribution, asrepresented the polydispersity index (PDI) (i.e., the weight averagemolecular weight/number average molecular weight (Mw/Mn), e.g. asdetermined by gel permeation chromatography). For example, in certainembodiments, the polyether alcohol compound (B) comprises a PDI of 1.15or less, alternatively of 1.1 or less.

In certain embodiments, the polyether alcohol compound (B) a molecularweight (Mw) of less than 5000, for example a Mw of from 10 to less than5000, alternatively from 10 to 4500, alternatively from 50 to 4000,alternatively from 100 to 3000, alternatively from 100 to 2000.

In these or other embodiments, the polyether alcohol compound (B)comprises a low level of residual unreacted alkoxylatable compound(b-1), e.g. alcohol compound (b-1) (i.e., un-alkoxylated alcohol). Forexample, in some embodiments, the polyether alcohol compound (B)contains less than 3 weight percent, alternatively less than 2 wt. %, orless, alternatively 1 wt. % percent or less, alternatively 0.5 wt. % ofresidual/unreacted alcohol compound (b-1). In certain embodiments, thecomposition comprises a mixture of more than one polyether alcoholcompound (B), such as 2, 3, 4, 5, or more individual polyether alcoholcompounds (B), which are independently selected.

The amount of components (A) and (B) in the composition may vary. Insome embodiments, for example, the composition comprises from 10 to 80wt. % of the polysiloxane (A), based on the total weight of thecomposition. Likewise, in these or other embodiments, the compositioncomprises from 10 to 95 wt. % of the polyether alcohol compound (B),based on the total weight of the composition. In specific embodiments,the composition comprises from 10 to 80, alternatively from 20 to 80,alternatively from 20 to 70, alternatively from 30 to 70 wt. % of thepolysiloxane (A), based on the total weight of the composition. In theseembodiments, the balance of the composition may comprise the polyetheralcohol compound (B) alone or, alternatively, may comprise a combinationof the polyether alcohol compound (B) with one or more additionalcomponents of the composition. For example, as will be better understoodin view of the method described below, the composition may comprise acatalyst, or a solvent or carrier vehicle. In some embodiments, however,the composition is free from, alternatively substantially free from, acatalyst. In these or other embodiments, the composition is free from,alternatively substantially free from cyclic siloxanes. In these orother embodiments, the composition comprises less than 1 wt. % solvent,based on the total weight of the composition. In other embodiments, thecomposition is free from, alternatively substantially free from,solvents or carrier vehicles (i.e., aside from component (B) itself).

In certain embodiments, the composition further comprises (C) anaminosilicon compound. Generally, the aminosilicon compound (C) isutilized to impart the D siloxy units indicated by subscript b, ifpresent, and/or the T siloxy units indicated by subscript c′, ifpresent, in the polysiloxane (A), as described below with reference tothe method of preparing the composition. Use of the aminosiliconcompound (C) when preparing the polysiloxane (A) and/or the compositionis optional. When utilized, some residual amount of the aminosiliconcompound (C) may be present in the composition, i.e., the aminosiliconcompound (C) may not be fully consumed in preparing the polysiloxane (A)and/or the composition.

The aminosilicon compound (C) includes a silicon-bonded substituentcomprising an amino group, which can become the substituent indicated byR′ in the polysiloxane (A), if present. Typically, the aminosiliconcompound (C) also includes silicon-bonded hydroxyl and/or hydrolysablegroups, such as alkoxy groups.

In specific embodiments, the aminosilicon compound (C) comprises,alternatively is, an aminosilane, for example an aminosilane of formulaR′R¹⁰ _(h)Si(OR¹⁰)_(3-h), where subscript h is 0 or 1, R′ is definedabove, and each R¹⁰ is an independently selected alkyl group having from1 to 18, alternatively from 1 to 16, alternatively from 1 to 14,alternatively from 1 to 12, alternatively from 1 to 10, alternativelyfrom 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4,carbon atoms. In one embodiment, subscript h is 0 and the aminosiliconcompound (C) is of formula R′Si(OR¹⁰)₃. One specific example of such anaminosilane is 3-propylaminotriethoxysilane. In another embodiment,subscript h is 1 and the aminosilicon compound (C) is of formulaR′R¹⁰Si(OR¹⁰)₂. One specific example of such an aminosilane is3-propylamino(diethoxy)methylsilane.

When the aminosilicon compound (C) is utilized and is of formulaR′Si(OR¹⁰)₃, at least some of the aminosilicon compound (C) utilizedgenerally hydrolyses and condenses to give a T siloxy unit in thepolysiloxane (A) indicated by subscript c′, i.e., of formulaR′SiO_(3/2).

Typically, each alkoxy group of the aminosilicon compound (C) fullyhydrolyzes and condenses to give such a T siloxy unit in thepolysiloxane (A). During preparation of the polysiloxane (A), whenutilized, the aminosilicon compound (C) may give partial condensateproducts in a reaction intermediary of the polysiloxane (A). When theaminosilicon compound (C) is utilized and is of formula R′Si(OR¹⁰)₃, thepartial condensate products are of formula (R′(OZ)_(q)SiO_(3-q/2)),where subscript q is independently 0, 1, or 2, and each Z isindependently H or R¹⁰.

When the aminosilicon compound (C) is utilized and is of formulaR′R¹⁰Si(OR¹⁰)₂, at least some of the aminosilicon compound (C) utilizedgenerally hydrolyses and condenses to give a D siloxy unit in thepolysiloxane (A) indicated by subscript b′, i.e., of formulaR′R²SiO_(2/2).

Typically, each alkoxy group of the aminosilicon compound (C) fullyhydrolyzes and condenses to give such a D siloxy unit in thepolysiloxane (A). During preparation of the polysiloxane (A), whenutilized, the aminosilicon compound may give partial condensate productsin a reaction intermediary of the polysiloxane (A). When theaminosilicon compound (C) is utilized and is of formula R′R¹⁰Si(OR¹⁰)₂,the partial condensate products are of formula R′R¹⁰(OZ)rSiO_(2-r/2),where subscript r is independently 0 or 1, and each Z is independently Hor R¹⁰.

Combinations of different aminosilicon compounds may be utilizedtogether as the aminosilicon compound (C).

The aminosilicon compound (C) is typically present in the composition inan amount of from 0 to 25, alternatively from 0 to 20, alternativelyfrom 0 to 15, wt. % based on the total weight of the composition.

As introduced above, the composition comprises a tunable liquidviscosity. In particular, the composition generally comprises aviscosity at 25° C. of from 100 to 800,000 cps. For example, in certainembodiments, the composition comprises a viscosity of from 185 cps to700,000 cps, e.g. depending on the particular polyether alcohol compound(B) selected, the ratio of polysiloxane (A) to the polyether alcoholcompound (B) utilized, the presence or absence of the aminosiliconcompound (C), etc. Moreover, as will be appreciated in view of themethod below, the ratio of —OX=polyether moiety to —OX═H within thepolysiloxane (A) (i.e., the capping ratio) may also be independentlyselected and controlled to provide the composition in a liquid form.Because the composition has a tunable liquid viscosity, the viscositycan be selectively controlled based on desired end use applications andproperties thereof.

A method of preparing the liquid silicone resin composition is alsoprovided. The method includes (I) combining together a solid siliconeresin, the polyether alcohol compound (B), and optionally theaminosilicon compound (C) to give a mixture comprising the polysiloxane(A), the polyether alcohol compound (B), and optionally the aminosiliconcompound (C). The method also includes (II) liquefying the mixturecomprising the polysiloxane (A) and the polyether alcohol compound (B),thereby preparing the liquid silicone resin composition. As describedbelow, in certain embodiments utilizing the aminosilicon compound (C),the aminosilicon compound (C) is incorporated during and/or after thestep of liquefying the mixture.

As will be appreciated from the description herein, the polyetheralcohol compound (B) is capable of liquefying the solid silicone resin,optionally without reacting therewith. As such, the solid silicone resinis typically a solid when combined with the polyether alcohol compound(B), optionally in the presence of a carrier vehicle, as describedbelow. The term “solid” is used herein with reference to the solidsilicone resin to describe such silicone as having a softening and/ormelting point above room temperature, such that, at room temperature,the silicone resin is solid or substantially solid.

The solid silicone resin has the following general formula:

(R¹ ₃SiO_(1/2))_(a)(R⁴ ₂SiO_(2/2))_(b)(R⁴SiO_(3/2))_(c)(SiO_(4/2))_(d),

where each R⁴ is independently selected from R¹ and —OR, with theproviso that R⁴ is selected from —OH and —OR in at least one T siloxyunit indicated by subscript c, and each R¹, R, and subscripts a, b, c,and d are as defined above.

With regard to the preceding formula, as will be appreciated by those ofskill in the art in view of the description herein, the solid siliconeresin utilized in the method forms the siloxane backbone of thepolysiloxane (A). As such, the description above with regard to the M,D, T, and Q siloxy units indicated by subscripts a, b, c, and d,respectively, of the polysiloxane (A) applies equally to the solidsilicone resin of the method. For example, in certain embodiments, thesolid silicone resin comprises an MQ ratio, i.e., a ratio of M siloxyunits indicated by subscript a to Q siloxy units indicated by subscriptd, of from 0.5 to 1.5 (a:d). In these or other embodiments, the ratio ofM siloxy units indicated by subscript a to Q siloxy units indicated bysubscript d is from 0.7 to 1.2 (a:d) in the solid silicone resin.However, as readily understood in the art, though the ranges ofsubscripts a, b, c, and d are applicable to both the solid siliconeresin and the polysiloxane (A), each of subscripts a, b, c, and d mayindependently differ between the solid silicone resin and thepolysiloxane (A). For example, when the method of preparing thecomposition involves liquefaction, certain siloxane bonds may be cleavedto give SiOZ moieties, where Z is independently H or alkyl. To that end,the polysiloxane (A) may have, for example, fewer Q siloxy units thanthe solid silicone resin on a mole fraction basis. For example, a Qsiloxy unit in the solid silicone resin may result in a T(OZ) siloxyunit (i.e., a T siloxy unit having three siloxane bonds and an SiOZgroup) in the polysiloxane (A) from cleaving one siloxane bond. The SiOZgroups may remain in the polysiloxane (A), or may condense with thepolyether alcohol compound (B) and/or the aminosilicon compound (C), ifutilized, to give a functional group in the polysiloxane (A) (i.e., apolyether group and/or an amino group). In certain embodiments, thesolid silicone resin has an SiOZ content of from greater than 0 to 10,alternatively from greater than 0 to 8, alternatively from greater than0 to 6, alternatively from 0.5 to 4, wt. % SiOZ groups.

Typically, the solid silicone resin has a weight-average molecularweight of from 2,000 to 30,000, such as from 3,000 to 30,000,alternatively from 4,000 to 30,000, alternatively from 4,000 to 25,000,alternatively from 5,000 to 25,000, alternatively from 5,000 to 20,000,alternatively from 6,000 to 20,000. As understood by those of skill inthe art, weight-average molecular weight may be readily determined inDaltons using triple-detector gel permeation chromatography (e.g. withlight-scattering, refractive index and viscosity detectors) against apolystyrene standard.

It will be appreciated that the polyether alcohol compound (B) utilizedin the method (e.g. to cap and/or liquefy the polysiloxane (A)) is thesame component as described above with respect to the polyether alcoholcompound (B) of the composition. As such, the description above withregard to the polyether alcohol compound (B), and the various portionsthereof, also applies equally to the method.

As introduced above, the method of preparing the liquid silicone resincomposition comprises combining the solid silicone resin and thepolyether alcohol compound (B), and optionally, any other componentsutilized (collectively, the “method components”), to prepare a mixturetherewith. As will be understood by those of skill in the art, there isgenerally no proactive step required beyond combining the reactioncomponents together, although certain processes, which are describedbelow, may be employed. Moreover, while one aspect of the methodincludes reacting the solid silicone resin and the polyether alcoholcompound (B) (e.g. via condensation reaction) to prepare thepolysiloxane (A) and thereby give the composition, it is to beappreciated that in another aspect, the method may be utilized toprepare the composition via simply liquefying the polysiloxane (A) inthe presence of the polyether alcohol compound (B), withoutreacting/capping the same.

Further, as described above, the aminosilicon compound (C) mayoptionally be utilized in the method. When utilized, the aminosiliconcompound (C) can be incorporated at any time of the method of preparingthe composition. For example, in one embodiment, the aminosiliconcompound (C) is combined with the solid silicone resin and the polyetheralcohol compound (B) such that the aminosilicon compound (C) is presentin the mixture. Alternatively or in addition, the aminosilicon compound(C) can be combined with the mixture after its formation. Further still,the aminosilicon compound (C) can be combined during and/or afterliquefaction of the mixture, as described below.

With regard to the method components, the solid silicone resin may beprepared or otherwise obtained, i.e., as a prepared resin. Methods ofpreparing MQ resins such as the solid silicone resin are known in theart, with suitable precursors and starting materials commerciallyavailable from various suppliers. Preparing the solid silicone resin,when part of the method, is typically performed prior to combining thesame with the polyether alcohol compound (B). The polyether alcoholcompound (B) may also be prepared as part of the method, or otherwiseobtained for use therein. In particular embodiments, the polyetheralcohol compound (B) is prepared via reacting (e.g. alkoxylating) thealkoxylatable compound (b-1) with the alkoxylation agent (b-2). Whenselecting the alkoxylation agent (b-2), e.g. where an alkylene oxide isutilized, one of skill in the art will appreciate that propylene oxideand/or butylene oxide may be used to increase the flexibility of theproduct of the alkoxylation and/or the condensation reaction of themethod, and thereby alter the viscosity by increasing the fluidity ofthe polyether alcohol compound (B) and, optionally, the polysiloxane (A)prepared therewith

Typically, the method components are combined in a vessel or reactor toprepare the composition. The method components may be fed together orseparately to the vessel, or may be disposed in the vessel in any orderof addition, and in any combination, as exemplified below. The methodmay further comprise agitating the mixture, e.g. to enhance mixing andcontacting together of the method components when combined. Suchcontacting independently may use other conditions, with (e.g.concurrently or sequentially) or without (i.e., independent from,alternatively in place of) the agitating, and will typically beimplemented to assist in preparing the polysiloxane (A) in the mixtureand/or liquefying the mixture. Other conditions may be utilized inaddition to, or in place of, those described herein, and may beresult-effective conditions for enhancing condensation, liquefaction,etc., in the course of the method.

The method may utilize any amount of the method components and, morespecifically, may comprise combining the solid silicone resin, thepolyether alcohol compound (B), and optionally the aminosilicon compound(C) in varying amounts or ratios contingent on desired properties of theresulting composition and/or characteristics of the starting materialsemployed. For example, the solid silicone resin and the polyetheralcohol compound (B) may be utilized in amounts configured to provide aspecific cap ratio (i.e., the molar ratio of silanol functionality ofthe MQ resin to hydroxyl functionality of the polyether alcohol compound(B)) of the polysiloxane (A) prepared therewith (e.g. a cap ratio offrom 0.25 to 1.0, such as from 0.5 to 0.75, etc.). Accordingly, as willbe understood by those of skill in the art, the solid silicone resin andthe polyether alcohol compound (B) may be utilized in a 1:≥1 molarratio, favoring either component. For example, the solid silicone resinand the polyether alcohol compound (B) may be utilized in a molar ratioof from 1:10 to 10:1, alternatively of from 1:5 to 5:1, alternatively offrom 1:2 to 2:1, alternatively of from 1:1.1 to 1.1:1. As shown, anexcess (e.g. slight excess, moderate excess, or gross excess) of eithercomponent can also be utilized.

The solid silicone resin, the polyether alcohol compound (B), andoptionally the aminosilicon compound (C) may be combined in any order,optionally under shear or mixing. For example, in some embodiments themixture is prepared by combining together the solid silicone resin andthe polyether alcohol compound (B), optionally with any additionalcomponents being utilized, e.g. the aminosilicon compound (C). Thecomponents may be combined in any order, simultaneously, or anycombinations thereof (e.g. in various multi-part compositions which areeventually combined with one another). Likewise, the mixture may beprepared in batch, semi-batch, semi-continuous, or continuous processes,unless otherwise noted herein. Typically, once combined, the componentsof the mixture are homogenized, e.g. via mixing, which may be performedby any of the various techniques known in the art using any equipmentsuitable for the mixing. Examples of suitable mixing techniquesgenerally include ultrasonication, dispersion mixing, planetary mixing,three roll milling, etc. Examples of mixing equipment include agitatedbatch kettles for relatively high-flowability (low dynamic viscosity)compositions, ribbon blenders, solution blenders, co-kneaders,twin-rotor mixers, Banbury-type mixers, mills, extruders, etc., whichmay be batch-type or continuous compounding-type equipment, and utilizedalone or in combination with one or more mixers of the same or differenttype.

In some embodiments, the solid silicone resin, the polyether alcoholcompound (B), and optionally the aminosilicon compound (C) are combinedin the presence of a carrier vehicle. The carrier vehicle is not limitedand is typically selected for based on the particular solid siliconeresin and/or polyether alcohol compound (B) being utilized, a desiredend use of the composition, etc. In general, the carrier vehiclecomprises, alternatively is, a solvent, a fluid, an oil (e.g. an organicoil and/or a silicone oil), etc., or a combination thereof.

In some embodiments, the carrier vehicle comprises a silicone fluid. Thesilicone fluid is typically a low viscosity and/or volatile siloxane. Insome embodiments, the silicone fluid is a low viscosityorganopolysiloxane, a volatile methyl siloxane, a volatile ethylsiloxane, a volatile methyl ethyl siloxane, or the like, or combinationsthereof. Typically, the silicone fluid has a viscosity at 25° C. in therange of 1 to 1,000 mm²/sec. Specific examples of suitable siliconefluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,octamethyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane, tetradecamethylhexasiloxane,hexadeamethylheptasiloxane,heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxanepentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane as well aspolydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes,polymethylphenylsiloxanes, polydiphenylsiloxanes, caprylyl methicone,hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone,and the like, as well as derivatives, modifications, and combinationsthereof. Additional examples of suitable silicone fluids includepolyorganosiloxanes with suitable vapor pressures, such as from 5×10⁻⁷to 1.5×10⁻⁶ m²/s.

In certain embodiments, the carrier vehicle comprises an organic fluid,which typically comprises an organic oil including a volatile and/orsemi-volatile hydrocarbon, ester, and/or ether. General examples of suchorganic fluids include volatile hydrocarbon oils, such as C₆-C₁₆alkanes, C₈-C₁₆ isoalkanes (e.g. isodecane, isododecane, isohexadecane,etc.), C₈-C₁₆ branched esters (e.g. isohexyl neopentanoate, isodecylneopentanoate, etc.), and the like, as well as derivatives,modifications, and combinations thereof. Additional examples of suitableorganic fluids include aromatic hydrocarbons, aliphatic hydrocarbons,alcohols having more than 3 carbon atoms, aldehydes, ketones, amines,esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides,and combinations thereof. Hydrocarbons include isododecane,isohexadecane, Isopar L (C₁₁-C₁₃), Isopar H (C₁₁-C₁₂), hydrogentatedpolydecene. Ethers and esters include isodecyl neopentanoate,neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate,diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3ethoxypropionate, propylene glycol methyl ether acetate, tridecylneopentanoate, propylene glycol methylether acetate (PGMEA), propyleneglycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyladipate, diisopropyl adipate, propylene glycol dicaprylate/dicaprate,octyl ether, octyl palmitate, and combinations thereof. It will beappreciated that some examples of the organic fluids above (e.g. glycolethers) may overlap in description with the polyether alcohol compound(B), which may itself be utilized as a carrier vehicle, or incombination with another carrier vehicle described herein. In someembodiments, the method is carried out free from, alternativelysubstantially free from, organic fluids meeting the description of thepolyether alcohol compound (B) (i.e., other than the polyether alcoholcompound (B) itself).

In some embodiments, the carrier vehicle comprises an organic solvent.Examples of organic solvents include those comprising an alcohol, suchas methanol, ethanol, isopropanol, butanol, and n-propanol; a ketone,such as acetone, methylethyl ketone, and methyl isobutyl ketone; anaromatic hydrocarbon, such as benzene, toluene, and xylene; an aliphatichydrocarbon, such as heptane, hexane, and octane; a halogenatedhydrocarbon, such as dichloromethane, 1,1,1-trichloroethane, andchloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile;tetrahydrofuran; white spirits; mineral spirits; naphtha;n-methylpyrrolidone; and the like, as well as derivatives,modifications, and combination thereof.

In certain embodiments, the carrier vehicle comprises a polar organicsolvent, such as a solvent compatible with water. Specific examples ofsuch polar organic solvents utilized in certain embodiments includemethanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol,2-butanone, tetrahydrofuran, acetone, and combinations thereof. Othercarrier vehicles may also be utilized in place of, in addition to, or incombination with, those described herein. In certain embodiments, thecarrier vehicle comprises, alternatively is, an aliphatic and/oraromatic hydrocarbon solvent such as xylenes, etc., a siloxane solventsuch as hexamethylene disiloxane (HMDSO), D4 or D5 cyclics or other suchsiloxanes, or a combination thereof. In other embodiments, the method iscarried out substantially free from certain solvents. For example, insome embodiments, the method is carried out free from, alternativelysubstantially free from, hexamethylene disiloxane (HMDSO), D4 cyclics,and/or D5 cyclics. In these or other embodiments, the method is carriedout free from, alternatively substantially free from benzene, toluene,ethylbenzene, and xylenes (i.e., BTEX solvents). In these or otherembodiments, the method is carried out free from, alternativelysubstantially free from aromatic solvents.

In certain embodiments, the solid silicone resin is combined with thecarrier vehicle prior to being combined with the polyether alcoholcompound (B) and optionally the aminosilicon compound (C). In otherembodiments, however, the polyether alcohol compound (B) is combinedwith the carrier vehicle prior to being combined with the solid siliconeresin (and optionally the aminosilicon compound (C)) or, alternatively,the components are combined at substantially the same time to give themixture. Parameters associated with conditions under which thesecomponents are combined (e.g. temperature, pressure, etc.) may also becontrolled. However, the method may be carried out at ambientconditions.

Typically, the solid silicone resin, the polyether alcohol compound (B),optionally the aminosilicon compound (C), and the carrier vehicle arecombined together at a temperature less than 45° C. (i.e.,cold-processed) to give the mixture. In some embodiments, however, thesolid silicone resin, polyether alcohol compound (B), optionally theaminosilicon compound (C), and the carrier vehicle are combined togetherat a temperature less than 40° C., alternatively less than 35° C.,alternatively less than 30° C., alternatively at around ambienttemperature.

In some embodiments, the method comprises reacting the solid siliconeresin and the polyether alcohol compound (B) to prepare the polysiloxane(A) in the mixture. In these or other embodiments, with the methodutilizes the aminosilicon compound (C), the method may further comprisereacting the solid silicone resin or a reaction intermediary formed byreacting the solid silicone resin and the polyether alcohol compound (B)with the aminosilicon compound (C) to prepare the polysiloxane (A).Generally, the aminosilicon compound (C) hydrolyzes and condenses togive a T siloxy unit having amino functionality in the polysiloxane (A).As introduced above, the reaction of the method may be generally definedor otherwise characterized as a condensation reaction, and certainparameters and conditions of the reaction may be selected by those ofskill in the art in view of the particular components being utilized.For example, in some such embodiments, the method comprises disposing acatalyst (i.e., a condensation catalyst) into the mixture. Condensationcatalysts, such as those based on tin (e.g. Sn octanoate) or bases (e.g.NaOAc, KOH, etc.), are known in the art, and will be selected based onthe method components being utilized. In other embodiments, however, themethod is carried out in the absence of any tin catalyst, e.g. toprovide the composition as a product free from tin, and thereby avoidlimitations associated with tin being carried into the finalcomposition.

When implemented in the method, the catalyst may be utilized in anyamount, which will be selected by one of skill in the art, e.g. based onthe particular catalyst selected, the concentration/amount of activecatalytic species thereof, the nature/type of solid silicone resinand/or polyether alcohol compound (B) selected, the reaction parametersemployed, the scale of the reaction (e.g. total amounts of the methodcomponents utilized, etc.), etc. The molar ratio of the catalyst to themethod components may influence the rate and/or amount of condensationto prepare the polysiloxane (A) in the mixture. Thus, the amount of thecatalyst as compared to the method components, as well as the molarratios therebetween, may vary. Typically, these relative amounts andmolar ratios are selected to maximize the reaction of the methodcomponents while minimizing the loading of the catalyst (e.g. forincreased economic efficiency of the reaction, increased ease ofpurification of the reaction product formed, etc.).

In certain embodiments, the catalyst is utilized in an amount of from0.000001 to 50 wt. %, based on the total amount of solid silicone resinutilized (i.e., wt./wt.). For example, the catalyst may be used in anamount of from 0.000001 to 25, alternatively from 0.00001 to 10,alternatively from 0.0001 to 5 wt. % based on the total amount of solidsilicone resin utilized. In some embodiments, the catalyst is utilizedin an amount sufficient to provide a ratio of catalytic tin tohydrolysable groups of the solid silicone resin compound of from 1:10 to1:1,000,000, alternatively from 1:50 to 1:1,000 alternatively from 1:100to 1:500. Such ratios may be a weight ratio (i.e., wt./wt.) or,alternatively, a molar ratio between the components. It will beappreciated that amounts and ratios outside of the ranges listed abovemay be utilized as well. For example, the catalyst may be utilized in astoichiometric amount (i.e., a supracatalytic amount), e.g. based on thetotal amount of the polyether alcohol compound (B) utilized in themixture.

The catalyst may be prepared or otherwise obtained (i.e., as a preparedcompound). Methods of preparing condensation catalysts (e.g. tincatalyst, acetate catalyst, etc.) are known in the art, using compoundsthat are commercially available from various suppliers. The catalyst maythus be prepared prior to the reaction of the solid silicone resin andthe polyether alcohol compound (B) (and optionally the aminosiliconcompound (C)), or in situ (i.e., during the reaction of thosecomponents, e.g. via combining components of the catalyst with themixture comprising the solid silicone resin and the polyether alcoholcompound (B). As such, in certain embodiments, the catalyst is preparedas part of the preparation method, i.e., the preparation method includespreparing the catalyst.

When a condensation reaction is desired, the method will typicallyfurther comprise exposing the mixture to one or more condensationconditions, such as elevated temperature, reduced pressure, reflux, etc.As such, the vessel or reactor may be heated or cooled in any suitablemanner, e.g. via a jacket, mantle, exchanger, bath, coils, etc., so asto allow for the reaction to be carried out at an elevated or reducedtemperature, pressure, etc., as described below. For example, based onthe nature of the condensation reaction, the condensation conditions mayinclude heating the mixture to an elevated temperature such as 100° C.,e.g. to promote condensation of the polyether alcohol compound (B) andthe solid silicone resin (and optionally the aminosilicon compound (C)).Similarly, the condensation conditions may include pulling a vacuum onthe reactor being utilized to subject the mixture to reduced pressure(e.g. from 35 to 300 mbar). In combination, the reduced pressure andelevated temperature may be utilized to distill water from the reaction,thereby driving the condensation toward completion by preventing thereverse reaction. One of skill in the art will appreciate that theparticular temperature and pressure being utilized will be selectedbased on the method components and carrier vehicle present in themixture, e.g. to provide efficient refluxing conditions withoutover-heating the mixture. For example, in various embodiments, thereaction is carried out at a reaction/condensation temperature of from23 to 200° C., such as from greater than ambient temperature (e.g.greater than 25° C.) to 200° C., alternatively greater than 25 to 180,alternatively greater than 25 to 165, alternatively greater than 25 to150, alternatively from 30 to 150, alternatively from 50 to 150,alternatively from 70 to 150, alternatively from 60 to 150,alternatively from 85 to 150, alternatively from 100 to 150,alternatively from 110 to 150° C. In certain embodiments, the reactiontemperature is selected and/or controlled based on the boiling point ofany one solvent or volatile diluent, such as when utilizing refluxingconditions. Additionally, a cosolvent such as toluene may be utilized toazeotrope water from the mixture.

In general, the reaction speed of the components in the mixture (i.e.,the condensation of the polyether alcohol compound (B) and the solidsilicone resin, and optionally the aminosilicon compound (C)) increasesas i) the reaction temperature increases, and ii) water is removed fromthe reaction system. As such, the necessary reaction time will beselected in view of the particulars of the mixture being reacted. Inexemplary embodiments, the reaction time (i.e., condensation/cappingtime, which may be monitored via visual inspection, spectroscopy (e.g.NMR, FT-IR, etc.), or other methods known in the art) may be on theorder of from 1 to several hours, such as from 1 to 10 hours,alternatively from 2 to 10, alternatively from 3 to 10, alternativelyfrom 4 to 10, alternatively from 4 to 8, alternatively from 4 to 6hours. However, longer and shorter reaction times my both be selected,e.g. in view of the sixe/scale of the reaction, and any particularcomponents utilized in the mixture.

In certain embodiments, the method comprises dissolving the solidsilicone resin in the carrier vehicle (i.e., solvent) to give a siliconeresin solution, and combining the silicone resin solution and thepolyether alcohol compound (B) to form the mixture. As introduced above,when the method utilizes the aminosilicon compound (C), the aminosiliconcompound (C) can be combined with the silicone resin, and/or with themixture. In these embodiments, e.g. when the carrier vehicle isutilized, the method typically further comprises removing the carriervehicle from the mixture once the polysiloxane (A) is prepared therein.More specifically, in such embodiments, liquefying the mixture comprisessolvent exchanging the solid silicone resin from the solvent/carriervehicle to the polyether alcohol compound (B), thereby preparing thecomposition. The solvent exchange is not particularly limited, and maysimply involve removing the carrier vehicle from the reactor (e.g. viadistillation). For example, in certain embodiments, the method comprisesheating the mixture to a temperature of from 60 to 150° C. under reducedpressure (i.e., ˜35 mbar) to remove the solvent and give thecomposition.

As will be appreciated from the description above and examples herein,the composition prepared via the method provides a liquefied combinationof the polysiloxane (A) and the polyether alcohol compound (B), andoptionally residual aminosilicon compound (C), if utilized and not fullyconsumed. The polysiloxane (A) may comprise a condensation reactionproduct of the solid silicone resin and the polyether alcohol compound(B) (and optionally the aminosilicon compound) or, alternatively, maysimply be a liquefied form the of the solid silicone resin (e.g. when nocapping/condensation of with the polyether alcohol compound (B) iscarried out).

The following examples, illustrating embodiments of this disclosure, areintended to illustrate and not to limit the invention. Unless otherwisenoted, all reactions are carried out under air, and all solvents,substrates, and reagents are purchased or otherwise obtained fromvarious commercial suppliers (e.g. Gelest, Acros, Sigma-Aldrich) andutilized as received.

Equipment and Characterization Parameters

The following equipment and characterization procedures/parameters areused to evaluate various physical properties of the compounds andcompositions prepared in the examples below.

Gel Permeation & Size Exclusion Chromatography (GPC/SEC)

SEC Instrumentation

SEC is performed on a Waters 2695 LC pump and autosampler with a flowrate set at 1 mL/min, and an injection volume set at 100 μL. SECseparation is carried out on 2 Agilent PIgel Mixed-D columns using aShodex RI-201 differential refractive index detector, each held at 35°C.

Sample Preparation

Samples are prepared in THE eluent to a concentration ˜5 mg/mLpolymer/resin. The solution is shaken on a flat-bed shaker at ambienttemperature for about 2 hours, and then filtered through a 0.45 um PTFEsyringe filter prior to injection.

Processing of Data

Agilent GPC software Cirrus version 3.3 is used for data collection andfor data reduction. A total of 16 polystyrene (PS) linear narrowmolecular weight standards from Agilent, having Mp values from 3752 to0.58 kg/mol, are used for molecular weight calibration. A 3^(rd) orderpolynomial is used for calibration curve fitting, and all molecularweight averages, distributions, and references to molecular weight areprovided as PS equivalent values.

FT-IR Analysis

FT-IR instrumentation details are set forth in Table 1 below.

TABLE 1 FT-IR Instrumentation Instrument: Nexus 670 Detector: DTGS KBrBeam splitter: Csl Scans: 64 Collection length: 77.18 sec Resolution:4.000

Sample Preparation

Sample Spectrum: Samples are weighed into a 1 cm IR quartz cuvette witha fitted stopper. A specific volume of CCl₄ is added to the cuvette, andthe sample mixed thoroughly by shaking. The sample is then measured byIR using the spectral parameters listed below.

Reference Spectrum: Following the sample measurement, approximately 0.5mL D₂O is added to the cuvette, and the sample mixed vigorously forapproximately 30 seconds before being allowed to phase separate. Theupper D₂O layer is removed, and the addition/mixing procedure repeatedto ensure thorough D₂O exchange. The sample is again allowed to phaseseparate, and the D₂O left in place. The sample is then again measuredby IR (deuterated sample).

Processing of Data

Spectral Subtraction: The deuterated sample spectrum is subtracted fromthe original sample spectrum to remove invariant features. If thesubtraction results showed discernible interference of the water signalat 3610 cm⁻¹ (i.e., little to no —COH present), then a spectrum of waterin CCl₄ is subtracted from the original subtraction.

After the subtraction(s), the maximum peak height of the 3690 cm⁻¹ bandis measured, and the results used in the following calculation todetermine ppm OH of the silanol signal:

${{ppm}{OH}} = {\frac{{{Peak}{height}} - {y{intercept}}}{slope} \times \frac{{{Sample}{wt}} + {{volume}{solvent}}}{{Sample}{wt}}}$

Viscosity Measurement

Brookfield Instrumentation

A Brookfield DV3T cone/plate Rheometer, maintained at 25° C. by waterrecirculation, is utilized with a CPA-40Z spindle and 0.50 mL materialvolume for measurement.

Sample Preparation and Procedure

A method based ASTM D 4287 is utilized with a leveled viscometer. Foreach series of samples, required parameters to the digital viscometerare entered and the position of sample cup adjusted in relation tospindle (cone), as specified by the manufacturer, to maintain requiredclearance. The sample cup is removed, and 0.5 mL of sample added to thecenter of the cup using a 1 mL syringe in such a manner that all airbubbles are excluded from the material. The sample is allowed toequilibrate at 25+/−0.1° C. The motor is started at the specified speed,and the digital readout of viscosity noted. Prior to samples, theinstrument is calibrated using a Standard 200 Fluid (viscosity close tosamples, if possible) as a control.

²⁹Si NMR

For ²⁹Si NMR, 2.5 to 3 g of each product prepared below and about 5 g ofsolvent (CDCl₃+Cr(acac)₃) were loaded into a 16 mm silicon free NMR tubeand the spectra were obtained as per conditions and instrumentation inTable 2 below:

TABLE 2 ²⁹Si NMR Instrumentation Parameter: ²⁹Si Instrument Agilent 500DD2 NMR Spectrometer NMR Probe 16 mm Si Free AutoX Probe SpectrometerField Strength 11.7 T Pulse Sequence S2PUL Number scans (nt): 64Acquisition Time (at): 1.0161 s Delay Time (d1): 13 s Pulse Width (pw)18 μs Solvent CDCl3 + Cr(acac)3 Decoupler modulation (dm) nny Decoupleroffset frequency (dof) −400 hz Decoupler modulation field (dmf) 8812 hzDecoupler sequence (dseq) Waltz16 Transmitter offset frequency (tof)−5006 hz

Materials

A brief summary is provided in Table 3 below, setting forth informationas to certain abbreviations, shorthand notations, and componentsutilized in the Examples.

TABLE 3 Materials Utilized Component Description Silicone Resin 1 (SR-1)MQ resin: M/Q ratio~0.94; Mw~3450; solids = 71.5% in xylene SiliconeResin 2 (SR-2) MQ resin: M/Q ratio~0.98; Mw~8550; solids = 71.54% inxylene Silicone Resin 3 (SR-3) MM^(Vi)Q resin: M/Q ratio~0.76; M^(Vi)content~0.05 (mole %); Mw~23,500; solids = 72.5% Silicone Resin 4 (SR-4)MM^(Vi)Q resin: M/Q ratio~0.62; M^(Vi) content~0.11 (mole %); Mw~25,000;solids = 65.3% Polyether Alcohol 1 (PA-1) Branched secondary alcoholethoxylate of trimethyl nonanol: EO~3; fn = 1 Polyether Alcohol 2 (PA-2)Branched secondary alcohol ethoxylate of trimethyl nonanol: EO~5; fn = 1Polyether Alcohol 3 (PA-3) Branched secondary alcohol ethoxylate oftrimethyl nonanol: EO~10; fn = 1 Polyether Alcohol 4 (PA-4) Dipropyleneglycol butyl ether: fn = 1; Mw = 363 Polyether Alcohol 5 (PA-5) EO/POglycol butyl ether: fn = 1; Mw = 272 Polyether Alcohol 6 (PA-6)C12-EO/PO glycol ether Polyether Alcohol 7 (PA-7) Block polyalkoxylate(PO-EO): fn = 3; Mw = 1652 Polyether Alcohol 8 (PA-8) Randompolyalkoxylate (PO-EO): fn = 3; Mw = 1030 Polyether Alcohol 9 (PA-9)EO/PO glycol butyl ether, fn = 1, Mw = 190 Condensation Catalyst 1 SnOctanoate Aminosilicon Compound 3-aminopropyltriethoxysilane

Example 1

246.7 g of Silicone Resin 1 and 79.93 g of Polyether Alcohol 1 wereloaded into a 1000 mL 4-neck flask. 0.15 g of Condensation Catalyst 1was added and the contents adjusted to 50 wt. % solids (SR+PA) byaddition of xylene (total weight=506.7 g). The flask was mixed with anoverhead stirrer at 200 rpm and then heated to 80° C. for 15 min. ADean-Stark trap was attached to the flask and the contents refluxed at140° C. for 4 hours, collecting the water of reaction. The flask wascooled to room temperature and rotovaped under vacuum at 100° C. toremove xylene. The product obtained was clear and had a Brookfieldviscosity of 1800 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜68%.

Example 2

226.0 g of Silicone Resin 1 and 93.75 g of Polyether Alcohol 2 wereloaded into a 1000 mL 4-neck flask. 0.15 g of Condensation Catalyst 1was added and the contents adjusted to 50 wt. % solids (SR+PA) byaddition of xylene (total weight=506.1 g). The flask was mixed with anoverhead stirrer at 200 rpm and then heated to 80° C. for 15 min. ADean-Stark trap was attached to the flask and the contents refluxed at140° C. for 4 hours, collecting the water of reaction. The flask wascooled to room temperature and rotovaped under vacuum at 100° C. toremove xylene. The product obtained was clear and had a Brookfieldviscosity of 1386 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜63%.

Example 3

760.5 g of Silicone Resin 2 and 223.7 g of Polyether Alcohol 1, wereloaded into a 1500 mL 4-neck flask. 0.3 g of Condensation Catalyst 1 wasadded and the contents adjusted to 75 wt. % solids (SR+PA) by additionof xylene (total weight=1018.5 g). The flask was mixed with an overheadstirrer at 200 rpm and then heated to 80° C. for 15 min. A Dean-Starktrap was attached to the flask and the contents refluxed at 140° C. for4 hours, collecting the water of reaction. The flask was cooled to roomtemperature and rotovaped under vacuum at 100° C. to remove xylene. Theproduct obtained was clear and had a Brookfield viscosity of 63,500 cps.The samples were analyzed by GPC, Si NMR, and FT-IR. The productobtained had a resin content of ˜70%.

Example 4

702.5 g of Silicone Resin 2 and 263.8 g of Polyether Alcohol 2 wereloaded into a 1500 mL 4-neck flask. 0.3 g of Condensation Catalyst 1 wasadded and the contents adjusted to 75 wt. % solids (SR+PA) by additionof xylene (total weight=1017.1 g). The flask was mixed with an overheadstirrer at 200 rpm and then heated to 80° C. for 15 min. A Dean-Starktrap was attached to the flask and the contents refluxed at 140° C. for4 hours, collecting the water of reaction. The flask was cooled to roomtemperature and rotovaped under vacuum at 100° C. to remove xylene. Theproduct obtained was clear and had a Brookfield viscosity of 15,600 cps.The samples were analyzed by GPC, Si NMR, and FT-IR. The productobtained had a resin content of ˜65%.

Example 5

330.5 g of Silicone Resin 1 and 122.2 g of Polyether Alcohol 4 wereloaded into a 1000 mL 4-neck flask. 0.15 g of Condensation Catalyst 1was added and the contents adjusted to 70 wt. % solids (SR+PA) byaddition of xylene (total weight=508.9 g). The flask was mixed with anoverhead stirrer at 200 rpm and then heated to 80° C. for 15 min. ADean-Stark trap was attached to the flask and the contents refluxed at140° C. for 4 hours, collecting the water of reaction. The flask wascooled to room temperature and rotovaped under vacuum at 100° C. toremove xylene. The product obtained was clear and had a Brookfieldviscosity of 1762 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜65%.

Example 6

322.7 g of Silicone Resin 1 and 127.3 g of Polyether Alcohol 5 wereloaded into a 1000 mL 4-neck flask. 0.15 g of Condensation Catalyst 1was added and the contents adjusted to 70 wt. % solids (SR+PA) byaddition of xylene (total weight=508.8 g). The flask was mixed with anoverhead stirrer at 200 rpm and then heated to 80° C. for 15 min. ADean-Stark trap was attached to the flask and the contents refluxed at140° C. for 4 hours, collecting the water of reaction. The flask wascooled to room temperature and rotovaped under vacuum at 100° C. toremove xylene. The product obtained was clear and had a Brookfieldviscosity of 46,400 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜64%.

Example 7

58.5 g of Silicone Resin 1, 57.4 g of Polyether Alcohol 3, and 25.6 g ofPolyether Alcohol 6 were loaded into a 500 mL 4-neck flask. 0.19 g ofCondensation Catalyst 1 was added and the contents adjusted to 70 wt. %solids (SR+PA) by addition of xylene (total weight=141.8 g). The flaskwas mixed with an overhead stirrer at 200 rpm and then heated to 80° C.for 15 min. A Dean-Stark trap was attached to the flask and the contentsrefluxed at 140° C. for 4 hours, collecting the water of reaction. Theflask was cooled to room temperature and rotovaped under vacuum at 100°C. to remove xylene. The product obtained was clear and had a Brookfieldviscosity of 185 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜41%.

Example 8

436 g of Silicone Resin 1 and 2574.9 g of Polyether Alcohol 7 wereloaded into a 5000 mL 4-neck flask. 0.9 g of Condensation Catalyst 1 wasadded and the contents adjusted to 45 wt. % solids (SR+PA) by additionof xylene (total weight=3013.5 g). The flask was mixed with an overheadstirrer at 200 rpm and then heated to 80° C. for 15 min. A Dean-Starktrap was attached to the flask and the contents refluxed at 140° C. for4 hours, collecting the water of reaction. The flask was cooled to roomtemperature and rotovaped under vacuum at 100° C. to remove xylene. Theproduct obtained was clear to hazy and had a Brookfield viscosity of 185cps. The samples were analyzed by GPC, Si NMR, and FT-IR. The productobtained had a resin content of ˜10%.

Example 9

291 g of Silicone Resin 1 and 716.6 g of Polyether Alcohol 7 were loadedinto a 2000 mL 4-neck flask. No condensation catalyst was added. Thecontents were adjusted to 90 wt. % solids (SR+PA) by addition of xylene(total weight=1007.6 g). The flask was mixed with an overhead stirrer at200 rpm and then heated to 60° C. for 15 min. The flask was cooled toroom temperature and rotovaped under vacuum at 100° C. to remove xylene.The product obtained was clear and had a Brookfield viscosity of 185cps. The samples were analyzed by GPC, Si NMR, and FT-IR. The productobtained had a resin content of ˜20%.

Example 10

246.8 g of Silicone Resin 1 and 704.1 g of Polyether Alcohol 8 wereloaded into a 2000 mL 4-neck flask. No condensation catalyst was added.The contents were adjusted to 90 wt. % solids (SR+PA) by addition ofxylene (total weight=950.8 g). The flask was mixed with an overheadstirrer at 200 rpm and then heated to 60° C. for 15 min. The flask wascooled to room temperature and rotovaped under vacuum at 100° C. toremove xylene. The product obtained was clear and had a Brookfieldviscosity of 185 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜20%.

GPC and FT-IR Analysis for Examples 1-10

The results of the GPC and FT-IR analysis for the initial MQ resins andthe compositions obtained in Examples 1-10 are set forth in Tables 4-6below.

GPC compositions were obtained by deconvolution of GPC spectra andcalibration of free MQ resin (SR) and free alcohol compound (PA).

Based on the amount of free alcohol (PA) calculated, remaining alcoholwas assumed to be reacted (capped) on to the MQ resin (SR), and MQ-OR isestimated assuming molar capping onto the MQ resin. For the FTIRresults, assuming Si—OH reduction is from capping of the alcohol, MQ-ORare overestimated compared to GPC. Based on this assumption, SiOH ppmfrom spectra are normalized to the initial MQ resin SiOH signal in eachcase, to estimate the reduction of SiOH signal to reaction with thealcohol compound.

TABLE 4 GPC Data for Initial MQ Resins of Examples 1-10 SR PA Vis- Ex-Wt. % Wt. % cosity GPC of MQ Resin (SR) ample (est.) (est.) (cps) Mn MwMz Mp PD 1 68 32 1800 2420 3370 5280 9180 1.39 2 63 37 1386 3390 45206120 8170 1.33 3 70 30 63500 3880 8470 19000 3150 2.18 4 65 35 156004550 7270 11900 6770 1.6 5 65 35 1762 2607 3360 4675 6507 1.29 6 64 3646400 2809 3750 5214 7166 1.33 7 32.8 67.2 185 Not Analyzed 8 10 9018450 4800 7930 11100 17880 1.65 9 20 80 505 4930 6830 7810 8610 1.39 1020 80 363 3830 4380 4740 5030 1.14

TABLE 5 GPC Data for Compositions of Examples 1-10 SR PA FinalComposition (GPC) Wt. % Wt. % Viscosity Free PA Free SR MQ-OR Example(est.) (est.) (cps) (%) (%) (%) 1 68 32 1800 26.0 57.8 16.2 2 63 37 138626.0 48.3 25.7 3 70 30 63500 28.0 66.6 5.4 4 65 35 15600 22.0 47.7 30.35 65 35 1762 34.0 63.5 2.5 6 64 36 46400 27.2 50.9 21.9 7 32.8 67.2 185Not Analyzed 8 10 90 18450 Overlap of MQ Resin/ 9 20 80 505 AlcoholSpectra 10 20 80 363

TABLE 6 FT-IR Data for Compositions of Examples 1-10 Final Composition(FT-IR) SR Wt. % PA Wt. % Viscosity OH Free PA Free SR MQ-OR Example(est.) (est.) (cps) (ppm) (%) (%) (%) 1 68 32 1800 5027.0 21.0 40.0 39.02 63 37 1386 1640.0 14.4 13.0 72.5 3 70 30 63500 3611.0 28.8 66.8 4.4 465 35 15600 444.0 10.2 7.1 82.7 5 65 35 1762 5673.0 26.6 45.1 28.3 6 6436 46400 3419.0 22.9 27.2 49.9 7 32.8 67.2 185 2239.0 34.8 12.7 31.7 810 90 18450 888.0 87.7 7.1 5.2 9 20 80 505 1807.0 75.7 14.4 10.0 10 2080 363 2265.0 78.7 18.0 3.3

Referring to the Tables 4-6 above, all compositions have >10 to 70 wt. %of MO resin (SR), either solubilized or partially grafted (capped) withalcohol/capping agents (PA) to give liquid silicone resin compositions.

Examples 11-13

Three compositions are prepared according to the procedures of Examples1-10 above, using Silicone Resin 2 and various alcohols/capping agents(PA) to prepare Examples 11-13, the details of which are set forth inTable 7 below, along with the Brookfield viscosity of the resultingcompositions.

TABLE 7 Components and Viscosities of Examples 11-13 Cap SR Wt. % PA Wt.% Viscosity Example M/Q Ratio PA Ratio (est.) (est.) (cps) 11 0.8 PA-1 162 38 8400 12 0.8 PA-2 1 56 44 2240 13 1 PA-3 1 44 56 18,750

The compositions were analyzed for % of capping via ²⁹Si NMR, theresults of which are shown in Table 8 below, where “I” designates aninitial sample, and “F” designates the final compositions prepared. InTable 8, M indicates an M siloxy unit; D indicates a D siloxy unit; Tindicates a T siloxy unit; Q indicates a Q siloxy unit; and Z isindependently H or alkyl. OZ indicates an SiOZ group in lieu of asiloxane bond.

TABLE 8 ²⁹Si NMR Analysis for Examples 11-13 M/Q Mol % Example M D(OZ,OZ) T(OZ) Q T(OH) Ratio Cap 11-I 33.7 0.4 14.8 41.4 14.8 0.8 — 11-F 37.8−0.1 17.5 38.7 17.5 1.0 0 12-I 40 −0.2 8.9 47.3 8.9 0.8 — 12-F 44.9 0.111.9 44.3 3.8 1.0 68.3 13-I 42.1 0.6 13.2 43 13.2 1.0 — 13-F 47 0 13.542.7 5.5 1.1 58.9

The compositions of Examples 11-13 were also analyzed via GPC againstpolystyrene standards, the results of which are shown in Table 9 below,where “I” designates an initial sample, and “F” designates the finalcompositions prepared.

TABLE 9 GPC Analysis for Examples 11-13 Example Peak RT (min) Mn Mw MzMp PD 11-I 13.7-17.8 3840 8430 18500 3090 2.19 11-F 13.6-17.8 3890 855019000 7080 2.2 12-I 14.1-17.5 3730 6520 11900 3130 1.75 12-F 14.3-17.54430 6720 10200 6520 1.52 13-I 14.6-17.0 4680 6230 8830 2970 1.33 13-F14.2-17.1 6190 9170 13600 8500 1.48

Examples 14-18

Five compositions were prepared according to the procedures of Examples1-10 above, using various MQ resins (SR) and capping agents (PA) toprepare Examples 14-18, the details of which are set forth in Table 10below, along with the viscosity of the resulting compositions.

TABLE 10 Components and Viscosities of Examples 14-18 SR Wt. % PA Wt. %Viscosity Example SR PA Cap Ratio (est.) (est.) (cps) 14 SR-3 PA-1 0.950.77 0.23 >700,000 15 SR-3 PA-2 0.95 0.72 0.28 695,300 16 SR-4 PA-1 0.950.79 0.21 >700,000 17 SR-4 PA-2 0.95 0.74 0.26 180,400 18 SR-1 PA-1 10.6 0.4 1060

Example 19

291.7 g of Silicone Resin 2 and 140 g of Polyether Alcohol 9 were loadedinto a 2000 mL 4-neck flask. No condensation catalyst was added. Theflask was rotovaped under a vacuum of 2-5 mm Hg at 60° C. to remove81.68 g of xylene. The product obtained was clear and had a Brookfieldviscosity of 1230 cps. The samples were analyzed by GPC, Si NMR, andFT-IR. The product obtained had a resin content of ˜60%.

Example 20

100 g of the product formed in Example 19 and 6 g Aminosilicon Compoundwere cold blended for 3 hours at 60 revolutions per minute (rpm) at roomtemperature for a loading of 10% Aminosilicon Compound based on theresin content of the product formed in Example 19.

Example 21

100 g of the product formed in Example 19 and 6 g Aminosilicon Compoundwere blended for 3 hours at 60 rpm and heated at 80° C. in a rotovap ata vacuum of 300 mm Hg.

Example 22

100 g of the product formed in Example 19 and 12 g Aminosilicon Compoundwere blended for 3 hours at 60 rpm and heated at 80° C. in a rotovap ata vacuum of 300 mm Hg.

The results of the GPC and FT-IR analysis for the products compositionsobtained in Examples 19-22 are set forth in Table 11 below.

TABLE 11 Mw and PD of Examples 19-22 Example Mw PD 19 8219 2.25 20 48651.799 21 5530 1.882 22 4197 1.6923

The products of Examples 19-22 were analyzed for siloxy unit content via²⁹Si NMR, the results of which are shown in Table 12 below. In Table 12,Z is H or alkyl; Me is methyl; NeoPentyl is (CH₃)₃CCH₂; A.S.C. indicatesAminosilicon Compound; X is independently H, a hydrocarbyl group Rhaving from 1 to 30 carbon atoms, or a polyether moiety formed by thePolyether Alcohol 9; and T′ indicates an H₂NCH₂CH₂CH₂SiO_(3/2) siloxyunit. The values in Table 12 are mole fractions.

TABLE 12 Siloxy unit content of Examples 19-22 Unit 19 20 21 22 A.S.C.Me₃SiOZ 0 0.11 0 0.25 0 Me₃SiO_(1/2) 42.15 40.47 40.36 39.74 0NeoPentylMe₂SiO_(1/2) 1.51 1.88 1.75 1.62 0 R′Si(OZ)₃ 0 0.25 0 0.7597.07 CH₃(OZ)₂SiO_(1/2) 0 0.82 0.59 1.46 2.93 CH₃(OZ)SiO_(2/2) 0 1.491.51 1.7 0 T′ 0 1.72 2.96 3 0 (OX)SiO_(3/2) 13.41 7.56 8.05 5.84 0SiO_(4/2) 42.93 45.69 44.79 45.65 0

The invention has been described in an illustrative manner, and it is tobe understood that the terminology which has been used is intended to bein the nature of words of description rather than of limitation.Obviously, many modifications and variations of the present inventionare possible in light of the above teachings. The invention may bepracticed otherwise than as specifically described.

1. A liquid silicone resin composition, said composition comprising: (A)a polysiloxane having the following formula:(R¹ ₃SiO_(1/2))_(a)(R²₂SiO_(2/2))_(b)(R′R²SiO_(2/2))_(b′)(R²SiO_(3/2))_(c)(R′SiO_(3/2))_(c′)(SiO_(4/2))_(d),wherein subscripts a, b, b′, c, c′, and d are each mole fractions suchthat a+b+b′+c+c′+d=1, with the provisos that 0<a<1, 0≤b<0.2, 0≤b′≤0.1,0<c<0.2, 0≤c′≤0.1, 0<d<1, and 0≤b′+c′≤0.1, and the ratio of subscript ato subscript d is from 0.5 to 1.5 (a:d); each R¹ is independentlyselected from hydrocarbyl groups having from 1 to 30 carbon atoms, —OH,and H; each R² is independently selected from R¹ and —OX, where each Xis independently H, a hydrocarbyl group R having from 1 to 30 carbonatoms, or a polyether moiety having the general formula—Y—R³(—[Y]_(j)—Z)_(i), wherein R³ is a substituted or unsubstitutedhydrocarbon segment, each Y is an independently selected oxyalkylenesegment of general formula (C_(n)H_(2n)O)_(m), where subscript m is from1 to 50 and subscript n is independently selected from 2 to 4 in eachmoiety indicated by subscript m, each Z is independently H or a resinoussilicone moiety, subscript i is from 0 to 8, and subscript j isindependently 0 or 1 in each moiety indicated by subscript i; and eachR′ comprises an independently selected amino group; and (B) a polyetheralcohol compound having the general formula HO—Y—R³(—[Y]_(j)—H)_(i),wherein each Y, R³, subscript i, and subscript j are as defined above.2. The liquid silicone resin composition of claim 1, wherein: (i) theratio of M siloxy units indicated by subscript a to Q siloxy unitsindicated by subscript d is from 0.7 to 1.2 a:d; (ii) subscript a isfrom 0.3 to 0.6; (iii) the sum of subscripts b and c is less than 0.2;(iv) subscript d is from 0.4 to 0.7; (v) the polysiloxane (A) comprisesa weight-average molecular weight (Mw) of from 2000 to 30,000; or (vi)any combination of (i)-(v).
 3. The liquid silicone resin composition ofclaim 1, wherein in the polysiloxane (A): (i) each R² is independentlyof formula —OX in the T siloxy units indicated by subscript c; (ii) X isthe polyether moiety in from 1 to 90 mole % of each R² of formula —OX;(iii) each R¹ is independently selected from alkyl and aryl groupscontaining 1-30 carbon atoms and H; or (iv) any combination of(i)-(iii).
 4. The liquid silicone resin composition of claim 1, whereinin the polysiloxane (A): (i) each R² is independently selected from R¹and hydrocarbyloxy groups of formula —OR; (ii) each R¹ is independentlyselected from alkyl and aryl groups containing 1 to 30 carbon atoms,—OH, and H; (iii) each R is independently selected from alkyl and arylgroups containing 1 to 30 carbon atoms; (iv) each R′ is independently offormula —(CH₂)_(g)N(H)_(f)R_(2-f), where each g is independently from 1to 30, f is 0, 1, or 2, and R is independently selected and definedabove; or (v) any combination of (i)-(iv).
 5. The liquid silicone resincomposition of claim 1, wherein the hydrocarbon segment R³ comprises:(i) a linear or branched hydrocarbon group having from 3 to 30 carbonatoms; (ii) an aromatic group; (iii) an ether group; (iv) an aminegroup; or (v) any combination of (i)-(iv).
 6. The liquid silicone resincomposition of claim 1, wherein: (i) the hydrocarbon segment R³comprises a branched hydrocarbon group having from 3 to 16 carbon atoms;(ii) subscript i is from 1 to 8; (iii) subscript j is 1 in each moietyindicated by subscript i; (iv) each oxyalkylene segment Y independentlyhas the formula (C₂H₄O)_(x)(C₃H₆O)_(y)(C₄H₈O)_(z), where subscript x isfrom 1 to 50, subscript y is from 0 to 50, and subscript z is from 0 to50, and where units indicated by subscripts x, y and z may be inrandomized or block form in the oxyalkylene segment; or (v) anycombination of (i)-(iv).
 7. The liquid silicone resin composition ofclaim 1, wherein: (i) each subscript i is 0, and each hydrocarbonsegment R³ independently comprises a linear or branched hydrocarbongroup having from 3 to 30 carbon atoms; (ii) each subscript i is 1, andeach hydrocarbon segment R³ independently comprises at least one groupselected from linear or branched hydrocarbon groups having from 3 to 30carbon atoms, phenols, tetrahydrofurans, alkyl amines, and alkoxygroups; or (iii) each subscript i is at least 2, and each hydrocarbonsegment R³ independently comprises at least one group selected fromlinear or branched hydrocarbon groups having from 3 to 30 carbon atoms,alkyl amines, polyamines, polyamides, polyaziridines, polyphenols, andpolyesters.
 8. The liquid silicone resin composition of claim 1, whereinthe polyether alcohol compound (B) comprises the alkoxylation reactionproduct of (b-1) an organic compound comprising an alkoxylatable grouphaving an O-, N-, or S-bonded hydrogen atom and (b-2) an alkylene oxideor polyoxyalkylene compound.
 9. The liquid silicone resin composition ofclaim 8, wherein: (i) the organic compound (b-1) is further defined asan alcohol compound comprising from 1 to 9 hydroxyl groups; (ii) thealkylene oxide or polyoxyalkylene compound (b-2) is selected fromethylene oxide, propylene oxide, butylene oxide, a combination thereof,or a polyoxyalkylene formed therefrom; or (iii) both (i) and (ii). 10.The liquid silicone resin composition of claim 8, wherein the polyetheralcohol compound (B) comprises: (i) a polydispersity index (PDI) lessthan 1.15; (ii) a molecular weight (Mw) of less than 5000; (iii) lessthan 2 wt. % unreacted alcohol compound (b-1), based on the total weightof the polyether alcohol compound (B); or (iv) any combination of(i)-(iii).
 11. The liquid silicone resin composition of claim 1,comprising: (i) from 10 to 80 wt. % of the polysiloxane (A), based onthe total weight of the composition; (ii) from 10 to 95 wt. % of thepolyether alcohol compound (B), based on the total weight of thecomposition; (iii) a viscosity at 25° C. of from 100 to 800,000 cps; or(iv) any combination of (i)-(iii).
 12. The liquid silicone resincomposition of claim 1, wherein the composition: (i) is free from tin;(ii) is free from cyclic siloxanes; (iii) comprises less than 1 wt. % ofsolvent, based on the total weight of the composition; or (iv) anycombination of (i)-(iii).
 13. A method of preparing the liquid siliconeresin composition of claim 1, said method comprising: combining togethera solid silicone resin and the polyether alcohol compound (B) to give amixture comprising the polysiloxane (A) and the polyether alcoholcompound (B), wherein the solid silicone resin has the followingformula:(R¹ ₃SiO_(1/2))_(a)(R⁴ ₂SiO_(2/2))_(b)(R⁴SiO_(3/2))_(c)(SiO_(4/2))_(d),where each R⁴ is independently selected from R¹ and —OR, with theproviso that R⁴ is selected from —OH and —OR in at least one T siloxyunit indicated by subscript c, and each R¹, R, and subscripts a, b, c,and d are as defined above; and liquefying the mixture, therebypreparing the liquid silicone resin composition.
 14. The method of claim13, further comprising reacting the solid silicone resin and thepolyether alcohol compound (B) via condensation to prepare thepolysiloxane (A) in the mixture.
 15. The method of claim 13, whereinmethod further comprises combining (C) an aminosilicon compound with thesolid silicone resin and the polyether alcohol compound (B), and/orwherein the method further comprises combining (C) an aminosiliconcompound with the mixture before and/or after liquefying the mixture.16. The method of claim 15, wherein the aminosilicon compound (C) hasthe formula R′R¹⁰ _(h)Si(OR¹⁰)_(3-h), where R′ comprises an amino group,each R¹⁰ is an independently selected alkyl group having from 1 to 18carbon atoms, and subscript h is 0 or
 1. 17. The method of claim 13,wherein the solid silicone resin and the polyether alcohol compound (B)are combined together in the presence of a solvent; wherein the methodfurther comprises dissolving the solid silicone resin in the solvent togive a silicone resin solution; and wherein combining the solid siliconeresin and the polyether alcohol compound (B) to form the mixture isfurther defined as combining the silicone resin solution and thepolyether alcohol compound (B).
 18. The method of claim 17, whereinliquefying the mixture comprises solvent exchanging the solid siliconeresin from the solvent to the polyether alcohol compound (B), andwherein the solvent exchanging is carried out: (i) at a temperature offrom 60 to 150° C.; (ii) under reduced pressure; (iii) underdistillation conditions to remove solvent; or (iv) any combination of(i)-(iii).
 19. The method of claim 17, wherein the solvent comprises:(i) xylenes; (ii) hexamethylene disiloxane; (iii)octamethylcyclotetrasiloxane (D4); (iv) decamethylcyclopentasiloxane(D5); or (v) any combination of (i)-(iv).
 20. The method of claim 13,wherein the liquid silicone resin composition: (i) is free from tin;(ii) is free from cyclic siloxanes; (iii) comprises less than 1 wt. % ofsolvent, based on the total weight of the composition; or (iv) anycombination of (i)-(iii).